Process and apparatus for preparing activated carbon



' July 18, 1939. R, H. TwlNlNc; 2,166,225

PRoQEs AND APPARATUS FOR' REPARING AGTIVATED CARBON Filed Aprila, 1957 i /I //z "Parental Janis, '1939 2,166,225

UNITED STATES PATENT oFFlcl-z PBUCESS AND APPARATUS FOR. PBEPABING ACTIVATED CARBON Ralph n. Twlnlng, Arden, nel., 'assigner to narco Corporation, Wilmington, Del., a corporation I of DelawareV Application April 2, 1937, serial No. 134.531 4 claims. (cr/zsz-sy The invention relates to an improved process -wood is in the midst of what is known as its exofor the manufacture of activated carbon and to thermic reactions. The wood turns black almost the apparatus therefor. lMore particularly, it rein an instant and large quantities of vapors are lates toa continuous process for the manufacture driven olf. The last material to be driven out 5 of activated carbon from wood or similar celluof the wood isan oily, resinous substance known 5 losicl material. y as wood tar. At the conclusion of the exothermic Heretofore; it has been the practice to use comreactions when the flow of gas from the retort merclal charcoal as' a carbonaceous material for becomes stagnant, the operator concludes that the production of activated carbon with little retheretort is olf and banks the lires preparatory lo gard to the conditions under which the distillato discharging the charcoal. At this time, howl0 tion was carried out. This involved alwaste` of ever, the charcoal is surrounded by an atmosphere heat since the charcoal was usually cooled down of tar in^the vapor phase. A peculiar property of after manufacture and was later h'eated in the charcoalis that as soon as the temperature stops activating process. Moreover, the cooling down rising itceases to give olf gas; and, as soon as it l5 allowed the pores of the. wood charcpal to' sorbl ceases to give oif'gas, it adsorbs the surrounding 16 tar vapor, thus clogging them with condensed gas and vapor with great rapidity. Consequently, tar, and allowed this tar to oxidize, accompanied the drop in temperature before discharging is sufby polymerization and condensation producing a ilcient to allow the charcoal to adsorb large quanhard resinous material which lsexceedingly detrititles of the tar vapor, cloggingthe pores which mental to the process of activation. would otherwise be clean and open. 'I'he contents 20 An object of this invention .is to produce a suof the retort are then discharged and transferred perior activated carbon from wood by a new conto sealed containers where they are cooled out tinuous process with recovery of all valuable byof contact with air for 48 hours. This cooling is products in condition for the 'moet economic utifollowed by conditioning in the presence of air lization. for at least 48 hours before loading for shipment. 25 Another object of this invention is to devise -a This conditioning is necessitated by the fact that new apparatus adapted for the continuous manu-g the material is subject to spontaneous combusfacture of activated carbon directly from wood tion, that is, exposure to air causes a rise in temin .three individually controlled steps, namely, Derature not infrequently tohthe point of ignipredrying of the wood, carbonization 'ofthe pretion. The rise in. temperature is due, to a great 3o dried wood, and activation ofthe charcoal so proextent, tothe oxidation of the tar content .of thev duced. y charcoal. During this oxidation, accompanied Another object of this invention ls to produce by polymerization and condensation. all the tar activated carbon which is superior to prior actiin the charcoal is converted to hard, resinous mavated carbone and which is especially adapted for terial very diflicult to remove even by heating to 35 use in the purification ofatllieousv mediums, auch high temperature. I f it is later attempted to es drnking'wteh y activate such charcoal, such attempts result in a Another object of this invention is to produce carbon of little activity. an activated carbon having a much higher e@- It( has beenproposed to produce activated car- 1 10 tivity than prior activated carbon; ae measured by bon from wood by svc-called continuous processes. 40

Phenol dsmfpll'. Y A However, these. processes have not been successother Objects 0f this invention will 111018 fully nu cmey because they failed to take con hereinafter appear.

In the commercial production M charcoal wgod sideration certain factors which are shown below is heated in closed retorts kilns or ovens nur to be essential. The exotlerrniic reaction -which 45 al1-valuable products are driven olf. Usually the occurs during the des Active nation is very highest temperature to which the wood is' carried diflicult to control for several reasons. One of is about 400e Q In the mt' stage of djstulatfonthese isthe fact that the moisture in the wood the temperature of the wood remains near 100 C., requires additional he to remove it- Hence x as free moisture is driven om Upon removal of vwhen the exothermlc reaction starts, the addi-- all free moisture-and endothermic stage begins, tional heat evolved carriesthe temperature far during which heat is gradually Supplied until the above the cracking temperature of the tar with temperature of the wood is raised from 100 C. deleterious results to` subsequent activation. An'-.

to about 270? C. At orl` about 270 Clthere is a Other 4Femm!!! is that the exothermlo reaction is g5 sudden change to a very vigorous activityand the very violent, frequently almost explosive in force, j

particularly if instigated by application of external heat.

My invention overcomes the disadvantages attending the prior processes above enumerated, of producing activated carbon from wood, namely,

the processes wherein charcoal is formed as an intermediate product and is allowed to cool in the manner described and is then heated up again in an activating process and the processes wherein the hot charcoal is immediately activated. My invention enables the production of large yields .i concentrated crude pyroligneous liquor which makes possible low-cost recovery of all by-products, it being well-known in the destructive distillation industry that the more diluted the pyroligneous liquor, the higher the cost of recovering its valuable ingredients. It enables a carefully controlled production of charcoal and of pyroligneous liquor. It enables the production of a relatively tar-free charcoal with open pores which is much more suitable for activation than prior charcoals. It enables the production of charcoal having a tremendously reduced pitch or secondary carbon content. It enables larger yields of better quality activated carbon, and a simple and low cost operation because the process is truly continuous and because of the saving of fuel due to the 4utilization of the heat liberated by the exothermic reaction of destructivev distillation. 'I'his inven- .tion involves the only known process which continuously gives maximum yields of chemicals in condition for lowest cost of recovery and also produces a greatly improved charcoal for activation and continuously carries out the activation.

In the following description of the invention, a typical process and apparatus to be used in conjunction therewith will be described in some detail. While specific means and process steps will be described, it will be obvious that equivalent means and process steps may be used without departing from the spirit of the invention. In connection with the description, reference is made to the`accompanying drawing which portrays a vertical sectional view of a suitable apparatus for carrying out the invention.

There is first selected wood which is comminuted to suitable size. Sawdust, shavings, hogged wood, small mill clippings, or the like, may be used, or whole wood may be reduced to a suitable state of fine division. The wood is placed into a hopper, whence it is continuously fed into and through a pre-drying zone in which the free water is substantially completely removed. The predryer may be heated by any suitable means, as by the waste gas from the activating furnace, to a suitable temperature. Moist wood requires considerable heat for predrying. While the temperatures used in predrying need not and must'not be very high (usually around 100-125 C.) a considerable number of B. t. u. must be furnished to dry the wood because of the high latent heat of water. On the contrary, warm, dry wood needs no heat added to bring about its carbonization, but it carbonizes itself and gives oi heat. The heat given off is just enough to bring warm, dry wood to carbonization; but not enough to dry the wood if its moisture content is over 1%. It is .preferred to -predry to a moisture content of 1/% or less.

Predrying and carbonizing are done separately, according to this invention. Otherwise the heat that must be furnished to bring about predrying will result in overheating during carbonization with detrimental results. Also', by separation of these steps, dilution of the pyroligneous acid with the water from the Wood is prevented. The cost of vrecovery of chemicals from the pyroligneous acid depends largely upon its concentration, the more concentrated it is the less the recovery cost. Still another reason for separation of these steps is that the sizes of equipment needed for predryv dryer may be kept under a slight pressure so that the wood is dried in an atmosphere of superheated steam instead of air. Hence, the wood may be dried at a relatively high temperature. This also gives the advantage of minimizing the size of the predryer, of utilizing more effectively the waste gas from the activator, and of introducing the wood to the carbonizer very hot. The temperature of predrying may vary from 100 .(.o 200 C., depending upon the pressure, rate of travel of wood, moisture content, etc. Usually it is preferred to have the wood at a temperature of around 200 C., when it has completed its travel through the predryer and as it is introduced into the carbonizer. The moisture liberated is removed through a pressure regulated valve.

The warm predried wood next enters a carbonizing zone by any suitable means which allows passage of material continuously but which prevents the gases or heat in the predryer from passing into the carbonizing zone and vice versa, and which prevents exposure of the wood to the air. The wood is fed continuously in such quantities that just the right temperature is maintained to keep the reaction going but not enough to raise the temperature to the cracking point of the tar oils. The carbonizer is a closed retort equipped with suitable means for removal of the products of carbonization (destructive distillation), and also preferably with means lfor thermostatically controlling the temperature of the wood undergoing carbonization. This latter means may comprise a thermostat connected to suitable cold air and hot gas sources, and is so adjusted as to control c the temperature of the retort very rapidly and within very close limits. The most important factor in the process is the proper control of temperature during carbonization. If it is allowed to rise too high, the charcoal isA diil'lcult if not impossible to activate.

The lower the temperature of carbonization is maintained. the better is the yield and quality of the pyroligneous acid and the better is the activated carbon produced. In practice, it is maintained as close to 308 C. as is possible.

As will thus be apparent, the Wood is predried and carbonized without any substantial contact with air or other oxidizing gas.

The lowest temperature at which destructive distillation (carbonization) of Wood takes place is 270` C. However, in carrying out my process, I have found that 30G-400 C. in the carbonizing zone is about the lowest working temperature .which is practical for large scale operation. The f in destructive distillation but rather cooling is used. The arrangement is made for adding heat in order to maintain exactly the right .temperature in case cooling is overdone. Itis highly preferred, however. to utilize an automatic thermostatic control for the cold air and hot gasso as to provide against suchdiiiiculties. Such a control automatically supplies the correct amount of cooling or heatinggas of the correct temperature and easily controls the temperature of the wood undergoing distillation (carbonization) for optimum results. The hot gases supplied in this manner may come from Ithe waste hot gases from the activator, as previously indicated. The heated gases from the cooling of the carbonizing retort may be utilized in any suitable manner to recover j the heat contained therein, as for example to pre-- dry the wood, to heat water to be used in forming steam for activation, etc.

The wood is maintained in the carbonizer until t it is completely transformed into charcoal and is free from any distillable products. As a result of the careful temperature control, the process delivers from the distillation retort chemicals in maximum yields at maximum concentration and charcoal truly tar-free and-open-pored to the activating unit. Furthermore. the charcoal is delivered continuously and hot to the activating v unit. The cost of conditioning and handling charture is that the activating zone receives the charcoal hot as it comes from the carbonizing zone which cresults not only in a great saving of heat in activation but also eliminates the costly and disadvantageous cooling.: conditioning and handling of the charcoal referred to above.

The activation vtemperature will be around 1000'J yC. to ll00 C. The activator is preferably heated externally by means of a combustion chamber. .-Stea or other activating gas is passed in so as to subs ntially illly the space not' occupied by the carbon and to provide a bath of steam' for each particle of carbon. The steam'may be under pressure if desired, in which case the discharge outlet for the activated carbon .is provided with a gas-tight valve of suitable character. Theactivating gas preferably moves countercurrentlyto the carbon undergoing activation. Activation of this specially preparedcharcoal is much cheaper than for ordinary charcoal. Less lheat is required, less time of exposure to the' activating gases-is needed. Higher yields-and al greater degree of activity result. a

The carbonizing and activating units are separated because of the great differences in conditions of'carbonization and activation. A combin- .ing of these umts would not result in a thorough carriesfout the aims of the invention. with a low usually high yields of wood by-products, and an 'exceptionally high grade of activated'carbon.

The activator preferably passes the carbon continuously from one end to the other and utilizes external heat from the .combustion of suitable' fuel, and internal steam, as described. Any suitable type of activating furnace may be used, but

it is highly preferred to use steam as the sole cooled' with later drying and grinding as desired. g()

'Referring now.to the accompanying drawing. i representsv the hopper in which the initial undried or wet wood is placed. It is then conveyed by worm 2 into the predryer 3. The worm is shown as not taking up all the space in the dryer, but the arrangement is such that predryer is sealed so as to maintain a desired steam pressure therein by suitable sealing means (not shown) at the left of the predryer and an exit valve -(not shown) at therightl or4 outlet end of the predryer controlled by a pressure regulator. essentially of steam, pass through-pipes indicated generally by. 4 to the exit end of the predryer. 'Ihe vpredryer isheatedfby gases from The gases from the drying, consistingv around the activator' 23 which pass upwardly through gate 21. As the wood reaches the righthand side of the predryer, it contains virtually no moisture and is 4at a temperature of 125 to 200 C. It then passes downwardly through barrel `valve 5 which rotates continuously' at a suitable speed in such` a. manner as to allow passage of wood into carbonizer 6 but does not allow gase- 4ous communication between the predryer'f and used, for any desired purpose, such asfto make activating lsteam. The condensed pyroligneous Aacid collects in pipe ii, while theuncondensed wood gas is passed outwardly and upwardly through pipe I2 and utilized in any desired manl ner;` The carbonizer t is a steel, cylindrical retort in a brick setting ij with a hollow'space i4 between the brick and the steel. There is provvided a thermostat 3| within'the 4carbonizer (at the carbondzing zone) Jwhich is so connected to hot gas valve I5 and to 4cold air valve II as to increase the opening of valve I6 and at the same time to decrease the opening of valve i5 uponV an elevationof the temperature within the car-v bonizing zone above the predetermined optimum point described above, and to decrease the opening of valve i6 and at the same time to increase the opening of valve i5 upon a decrease 'of the temperature in thel carbonizing zone below the predetermined 'optimum point. Pyrometers (not shown) may, if desired, be connected to suitable points in the carbonizer, including one at the point where the thermostat is situated. A suitable exhaust fan (not shown) is connected to the Yexit end i1 of the retort jacket or hollow space I4, to thereby induce a draft around the carbonizer whenever either valve I5 or IIiv is open. Valves I5 and IE are arranged, so that as I5 is opened, I6 is closed, and so that as I6 is opened I5 is closed.

The wood passes downwardly through the carbonizer in a continuous manner and initiates its own exothermic carbonizing and destructive distillation reactions which are controlled in the manner described above. AsI the wood nears the bottom of the carbonizer 6 it will have been transformed into nearly pure charcoal. It then passes continuously through barrel valve I8 into the activator 23. Barrel valve I8 is similar to barrel valve 5 previously described and permits no gases to intercommunicate between the activator 23 and the carbonizer 6 but allows the passage of the hot charcoal from the carbonizer 6 into the activator 23.

Steam is admitted to the activator by means of steam inlet I9. It passes into steam chest which extends the length of the activatorl and permits the steam to pass upwardly by means of a series of small holes (not shown) preferably extending the full length of the combustion furnace, through the carbon which is being passed to the left by means of Worm 2|, and to thereby intimately contact the carbon particles. The steam and gases formed by the activation process pass outwardly through pipe 22, which may be provided wth a suitable pressure regulating valve (not shown) if desired so as to maintain th activation under pressure.'

The activation process will be corripleted when the carbon has passed all the way to the left where it is discharged through outlet Mas the final product. If the activator is under pressure, lthis outlet will be provided with a barrel valve similar to barrel valves I8 and 5 previously described.

The activator 23 is heated externally by a combustion chamber 25. The combustion gases, after passing around activator 23, pass upwardly into passage 26. Thence, they are available forl passage to the space I4 around the carbonizer if valve I5 should open. They also pass upwardly through gate 21, which allows them to circulate around the predryer in amount sufficient to predry the wood at the correct temperature. Gate 21 may be thermostatically controlled byl means of a thermostat suitably disposed in predryer 3. These gases, after passing aroundthe predryer, pass upwardly and out exit stack 28. The remaining combustion gases pass outwardly to the left through exit-29, whence they may be utilized vin any desired manner for recovery of the heat contained in them.

The whole assembly is preferably mounted in a brick setting as shown in the section. The carbonizing retort is preferably disposed, as shown, at the right of the main brick setting in a brick setting I3, at least part of which is in dividual to it, but the Whole assembly may, if desired, be placed in one brick setting which would go straight up en the right side'of the carbonlzing retort so as to encompass the right ends of the predryer and activator. I

The arrangement shown is very convenient.

the predryer being placed in the upper portion of the brick setting, over the activating means and combustion chamber, and the carbonizer being-disposed'so that its charging end is in intimate relation toK the discharge end of the predryer and so that its discharge end is in intimate relation to the charging end of the activator.

By the process described, I am able to produce a superior grade of activated carbon, which is highly suited for liquid treatment, such as reiining of sugar, purification of drinking water by removal of tastes and odors therefrom, etc. It may be produced with an unusually high phenol adsorptive power, namely, a phenol number over 8.0 and as high, for example, as 11, or higher in the granular form (see Baylis Elimination of Taste and Odor in Water, 1935, page 197) and a phenol value below 15 and as low, for example, as 1l, or lower in the powdered -form (Baylis, 10c. cit. pp. 182-184) While speciiicmeans and process steps have been vdescribed,"these are intended only as illustrative and not as limiting the invention, which is to be limited only as defined in the appended claims. In place of admitting cold air around the carbonizng retort, cooling may be eiected by any suitable means, such as passing an inert cooling gas such as carbon dioxide or waste ue gases through the wood undergoing distillation or carbonization. The activation may be effected with -any suitable gas, including steam, chlorine, carbon dioxide, or even an oxidizing gas such as air, although steam is preferred.

The term "wood as used in this specification is intended to include equivalent cellulosic material, as for example coconut shells and the like.

In the claims, the term continuous" is intended to mean a process wherein the material is continually and'uninterruptedly moving in all parts of the apparatus as distinguished from an intermittent or batch process.

What is claimed is as follows:

1. Apparatus for the continuous manufacture of activated carbon from cellulosic material comprising, in combination, a predryer, a carbonizer, means for transferring dried cellulosic material from the predryer to the carbonizer and to prevent substantial intercommunlcation of gases.

therebetween, means for cooling the carbonizer and maintaining its temperature at not over 400 C., an activator, and means for transferring carbonized cellulosic material from the Vcarbonizer to the activ-ator and to prevent substantial intercommunication of gases therebetween.

2. Apparatus for the continuous manufacture of activated carbon from cellulosic material comprising, in combination, a predryer.. a carbond izer, means for transferring dried cellulosic `materia] from the predryer to the carbonizer and to prevent substantial intercommunication of gasesv therebetween, said carbonizer having means, including a heat exchange surface in contact with a cooling medium, for maintaining its temperature at not over 400 C., means for supplying a cooling medium to the heat exchange surface of the carbonizer, an activator, and 'means for' transferring carbonized cellulosic material from the carbonizer to the activator and to prevent substantial intercommunication of gases therebetween.

3. A continuous process of preparing activated carbon which comprises predrying comminuted cellulosic material to a moisture content of not over 1% in a predrying zone, transferring the hot dried cellulosic material without contact with air and without substantial lofssof heat to a carbonizing zone and completelycarbonizing it while preventing intercommunication of gases between said predrying zone and said cabonizing zone, transferring the hot charcoal so produced without contact with air and without substantial loss of heat to an activating zone and activating it while preventing intercommunication of gases between said activating zone and said carbonizing zone.

4. A continuous process ot preparing activated carbon which comprises predrying comminuted ceilulosic material in a predrying sone to a moisture content of not over 1%, transferring the hot dried cellulosic material without contact with air ,and without substantial loss of heat to a carbonizing zone and completely carbonixing it while` m preventing the vapors of distillation from conannessa man u wimax@ meel-m m 'the drying zone and ,while maintaining the material by cooling at a temperature of substantially 30o-400' C.,

transferring the hot charcoal so produced with- -out contact with air and without substantial loss of heat to an activating zo'ne and activating it while preventing intercommunication of gases between said activating :one and said carbonizing i RALPH H. TWINING. 

